US20140332758A1

US20140332758A1 - Donor-acceptor compounds with nitrogen containing polyaromatics as the acceptor

Info

Publication number: US20140332758A1
Application number: US13/890,437
Authority: US
Inventors: Raymond Kwong; Sui Tung Lam; Chi Hang Lee
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2013-05-09
Filing date: 2013-05-09
Publication date: 2014-11-13
Also published as: JP6468723B2; JP2014218499A; US9537106B2; KR102189766B1; KR20140133435A; JP2019065289A

Abstract

Donor-acceptor compounds with nitrogen containing polyaromatics as the acceptor with emission originated from the charge transfer (CT) state is disclosed. The donor-acceptor compound is provided that has the structure of Formula 1 shown below:

wherein X₁to X₁₂is independently selected from the group consisting of C—R and N, wherein at least one of X₁to X₁₂is N, wherein each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and at least one of the R comprises a donor group with at least two electron-donating nitrogens.

Description

The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

The present invention relates to organic light emitting devices. More specifically, the present disclosure pertains to luminescent materials comprising donor-acceptor compounds with nitrogen containing polyaromatics as the electron acceptor for use as emitters in organic light emitting diodes.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:
In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
As used herein, the phrase “electron acceptor” means a fragment that can accept electron density from an aromatic system, and the phrase “electron donor” means a fragment that donates electron density into an aromatic system.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY OF THE INVENTION

Donor-acceptor compounds with nitrogen containing polyaromatics as the acceptor may be efficient emitters with emission originated from the charge transfer (CT) state. The emission can be tuned by varying the strength of the donor-acceptor interaction and the resulting energy of the CT state. The compounds may be used as emitters in OLED. According to an embodiment, a compound is provided that has the structure of Formula 1 shown below:
wherein X₁to X₁₂is independently selected from the group consisting of C—R and N;
wherein at least one of X₁to X₁₂is N;
wherein each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and at least one of the R comprises a donor group with at least two electron-donating nitrogens.
According to another embodiment, a first device comprising a first organic light emitting device is also provided. The first device can include an anode, a cathode, and an organic emissive layer disposed between the anode and the cathode. The organic emissive layer can include a compound of Formula 1, wherein X₁to X₁₂is independently selected from the group consisting of C—R and N; at least one of X₁to X₁₂is N; each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein at least one of the R comprises a donor group with at least one electron-donating nitrogen.
The first device can be a consumer product, an organic light-emitting device, and/or a lighting panel.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIG. 3 shows Formula 1 as disclosed herein.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.
The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference. As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant carbon.
It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, i.e. P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).
On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the thermal population between the triplet states and the singlet excited states. Compounds that are capable of generating E-type delayed fluorescence are required to have very small singlet-triplet gaps. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A distinctive feature of TADF is that the delayed component increases as temperature rises due to the increased thermal energy. If the reverse intersystem crossing rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding the spin statistics limit for electrically generated excitons.
It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, i.e. P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).
On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the thermal population between the triplet states and the singlet excited states. Compounds that are capable of generating E-type delayed fluorescence are required to have very small singlet-triplet gaps. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A distinctive feature of TADF is that the delayed component increases as temperature rises due to the increased thermal energy. If the reverse intersystem crossing rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding the spin statistics limit for electrically generated excitons.
E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (ΔE_S-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is often characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds often results in small ΔE_S-T. These states may involve CT states. Often, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (ΔE_S-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is often characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds often results in small ΔE_S-T. These states may involve CT states. Often, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
According to an embodiment, donor-acceptor compounds with unexpected CT emission properties are provided. The donor has two electron donating nitrogens. The acceptor moiety is based on electron deficient nitrogen containing triphenylene.
Donor-acceptor compounds with CT emissions may be useful in high efficiency delayed fluorescence OLED (Appl. Phys. Lett. 2012, 98, 083302; Nature Photonics, 2012, 6, 253; Nature 2012, 492, 234; Chem. Commun. 2012, 48, 11392; Angew. Chem. Int. Ed. 2012, 51, 11311; J. Am. Chem. Soc., 2012, 134, 14706; Chem. Commun. 2012, 48, 9580). The electron acceptors used are triazene or cyano groups. While these groups are strongly electron deficient, making the design of strong donor-acceptor strength easy, OLEDs incorporating them may not be very stable because of the lack of electron delocalization in these acceptors. In this invention, we use a high triplet energy polyaromatic system, namely, triphenylene with one or multiple nitrogens in the ring to render electron acceptor with high triplet energy. High triplet energy is important in order to obtain blue emission.
Triphenylene is a high triplet energy polyaromatic compound. Triphenylene with one or multiple nitrogens is electron deficient and can be used as an acceptor. We observed donor-acceptor emissions from a series of donor-acceptor compounds using azatriphenylene as the acceptor. The results are shown in Table 2 below.
According to a preferred embodiment, a donor-acceptor compounds having triphenylene with one or more nitrogens in the ring as an electron acceptor that are unexpectedly suited as delayed fluorescence emitters are disclosed. Such a compound has the structure according to Formula 1 shown below:
wherein X₁to X₁₂is independently selected from the group consisting of C—R and N;
wherein at least one of X₁to X₁₂is N;
wherein each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
at least one of the R comprises a donor group with at least two electron-donating nitrogens.
In some embodiments, the donor-acceptor compound is selected from the group consisting of
wherein R₁to R₁₂are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
at least one of R₁to R₁₂is
wherein L is a linker,
m is 1 or 0,
n≧1; and
wherein Donor is an electron donating group containing at least two electron-donating nitrogens and Donors can be different when n>1.
In some more specific embodiments, Donor is selected from the group consisting of:
wherein S₁to S₇represent mono, di, tri, tetra or penta substitutions with hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
The linker L can be one of
wherein A₁to A₂represent mono, di, tri or tetra substitutions with hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some more specific embodiments, the donor-acceptor compound can be one of
In other embodiments S₁to S₇and A₁-A₂are H. The resulting compounds are denoted as Compound No.-H. For example, Compound 1-H is
According to another embodiment, the donor-acceptor compound has the structure according to Formula 1 as defined above but at least one of the R comprises a donor group with at least one electron-donating nitrogen.
According to another aspect of the present disclosure, a first device that includes a first organic light emitting device is provided. The organic light emitting device includes an anode, a cathode, and an organic emissive layer disposed between the anode and the cathode. The organic emissive layer comprises a first emitting compound having the structure according to Formula 1, and its variations as described herein.
The first emitting compound has the structure according to the formula:
wherein X₁to X₁₂is independently selected from the group consisting of C—R and N;
at least one of X₁to X₁₂is N;
each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein at least one of the R comprises a donor group with at least one electron-donating nitrogen.
In some specific embodiments, the first emitting compound is selected from the group consisting of
wherein R₁to R₁₂are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
at least one of R₁to R₁₂is
wherein L is a linker,
m is 1 or 0,
n≧1; and
wherein Donor is an electron donating group containing at least one electron-donating nitrogen and Donors can be different when n>1.
In some embodiments, the Donor is selected from the group consisting of:
wherein S₁to S₇represent mono, di, tri, tetra or penta substitutions with hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In the first device according to some embodiments, L is one of
wherein A₁to A₂represent mono, di, tri or tetra substitutions with hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In the first device according to other embodiments, the first emitting compound is one of
In some other embodiments of the first device, S₁to S₇and A₁-A₂are H. The resulting compounds are denoted as Compound No.-H. For example, Compound 1-H is
The first device emits a luminescent radiation at room temperature when a voltage is applied across the organic light emitting device, wherein the luminescent radiation comprises a delayed fluorescence process. In the first device, the emissive layer can further comprises a first phosphorescent emitting material. In other embodiments, the emissive layer further comprises a second phosphorescent emitting material. The emissive layer further comprises a host material,
In some embodiments, the first device emits a white light at room temperature when a voltage is applied across the organic light emitting device by using, for example, Compound 9-H and Compound 4-H as the emitters. In some embodiments, the first emitting compound emits a blue light with a peak wavelength of about 400 nm to about 500 nm, for example Compound 9-H, Compound 15-H, Compound 129-H and Compound 457-H. In some embodiments, the first emitting compound emits a yellow light with a peak wavelength of about 530 nm to about 580 nm, for example Compound 4-H and Compound 12-H.
According to another aspect of the present disclosure, the first device comprises a second organic light emitting device, wherein the second organic light emitting device is stacked on the first organic light emitting device. The first device can be a consumer product. The first device can be an organic light-emitting device. The first device can be a lighting panel.
According to another embodiment of the first device, at least one of the R comprises a donor group with at least two electron-donating nitrogens.
In yet another aspect of the present disclosure, a formulation that includes a compound according to Formula 1 is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, an electron transport layer material (see below).
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphryin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and sliane derivatives; a metal oxide derivative, such as MoO_x; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to, the following general structures:
Each of Ar¹to Ar⁹is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar¹to Ar⁹is independently selected from the group consisting of:
k is an integer from 1 to 20; X¹⁰¹to X¹⁰⁸is C (including CH) or N; Z¹⁰¹is NAr¹, O, or S; Ar¹has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:
Met is a metal, which can have an atomic weight greater than 40; (Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹and Y¹⁰²are independently selected from C, N, O, P, and S; L¹⁰¹is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In another aspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

Host:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³and Y¹⁰⁴are independently selected from C, N, O, P, and S; L¹⁰¹is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N. In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y¹⁰³-Y¹⁰⁴) is a carbene ligand.
Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atome, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, host compound contains at least one of the following groups in the molecule:
wherein R¹⁰¹to R¹⁰⁷is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X¹⁰¹to X¹⁰⁸is selected from C (including CH) or N; and Z¹⁰¹and Z¹⁰²is selected from NR¹⁰¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L¹⁰¹is an another ligand, k′ is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
wherein R¹⁰¹is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar¹to Ar³has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X¹⁰¹to X¹⁰⁸is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L¹⁰¹is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 1 below. Table 1 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.

TABLE 1

MATERIAL	EXAMPLES OF MATERIAL	PUBLICATIONS

Hole injection materials

Phthalocyanine and porphryin compounds		Appl. Phys. Lett. 69, 2160 (1996)

Starburst triarylamines		J. Lumin. 72-74, 985 (1997)

CF_xFluorohydrocarbon polymer		Appl. Phys. Lett. 78, 673 (2001)

Conducting polymers (e.g., PEDOT:PSS, polyaniline, polypthiophene)		Synth. Met. 87, 171 (1997) WO2007002683

Phosphonic acid and sliane SAMs		US20030162053

Triarylamine or polythiophene polymers with conductivity dopants		EP1725079A1





Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides		US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009

n-type semiconducting organic complexes		US20020158242

Metal organometallic complexes		US20060240279

Cross-linkable compounds		US20080220265

Polythiophene based polymers and copolymers		WO 2011075644 EP2350216

Hole transporting materials

Triarylamines		Appl. Phys. Lett.
(e.g., TPD, α-NPD)		51, 913 (1987)
		U.S. Pat. No.
		5,061,569
		EP650955
		J. Mater. Chem.
		3, 319 (1993)
		Appl. Phys. Lett.
		90, 183503
		(2007)

		Appl. Phys. Lett. 90, 183503 (2007)

Triaylamine on spirofluorene core		Synth. Met. 91, 209 (1997)

Arylamine carbazole compounds		Adv. Mater. 6, 677 (1994), US20080124572

Triarylamine with (di)benzothiophene/ (di)benzofuran		US20070278938, US20080106190 US20110163302

Indolocarbazoles		Synth. Met. 111, 421 (2000)

Isoindole compounds		Chem. Mater. 15, 3148 (2003)

Metal carbene complexes		US20080018221

Phosphorescent PLED host materials

Red hosts

Arylcarbazoles		Appl. Phys. Lett. 78, 1622 (2001)

Metal 8-hydroxyquinolates (e.g., Alq₃, BAlq)		Nature 395, 151 (1998)

		US20060202194

		WO2005014551

		WO2006072002

Metal phenoxybenzothiazole compounds		Appl. Phys. Lett. 90, 123509 (2007)

Conjugated oligomers and polymers (e.g., polyfluorene)		Org. Electron. 1, 15 (2000)

Aromatic fused rings		WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065

Zinc complexes		WO2010056066

Chrysene based compounds		WO2011086863

Green hosts

Arylcarbazoles		Appl. Phys. Lett. 78, 1622 (2001)

		US20030175553

		WO2001039234

Aryltriphenylene compounds		US20060280965

		US20060280965

		WO2009021126

Poly-fused heteroaryl compounds		US20090309488 US20090302743 US20100012931

Donor acceptor type molecules		WO2008056746

		WO2010107244

Aza-carbazole/DBT/DBF		JP2008074939

		US20100187984

Polymers (e.g., PVK)		Appl. Phys. Lett. 77, 2280 (2000)

Spirofluorene compound		WO2004093207

Metal phenoxybenzooxazole compounds		WO2005089025

		WO2006132173

		JP200511610

Spirofluorene-carbazole compounds		JP2007254297

		JP2007254297

Indolocabazoles		WO2007063796

		WO2007063754

5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)		J. Appl. Phys. 90, 5048 (2001)

		WO2004107822

Tetraphenylene complexes		US20050112407

Metal phenoxypyridine compounds		WO2005030900

Metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands)		US20040137268, US20040137267

Blue hosts

Arylcarbazoles		Appl. Phys. Lett, 82, 2422 (2003)

		US20070190359

Dibenzothiophene/ Dibenzofuran-carbazole compounds		WO2006114966, US20090167162

		US20090167162

		WO2009086028

		US20090030202, US20090017330

		US20100084966

Silicon aryl compounds		US20050238919

		WO2009003898

Silicon/Germanium aryl compounds		EP2034538A

Aryl benzoyl ester		WO2006100298

Carbazole linked by non- conjugated groups		US20040115476

Aza-carbazoles		US20060121308

High triplet metal organometallic complex		U.S. Pat. No. 7,154,114

Phosphorescent dopants

Red dopants

Heavy metal porphyrins (e.g., PtOEP)		Nature 395, 151 (1998)

Iridium(III) organometallic complexes		Appl. Phys. Lett. 78, 1622 (2001)

		US2006835469

		US2006835469

		US20060202194

		US20060202194

		US20070087321

		US20080261076 US20100090591

		US20070087321

		Adv. Mater. 19, 739 (2007)

		WO2009100991

		WO2008101842

		U.S. Pat. No. 7,232,618

Platinum(II) organometallic complexes		WO2003040257

		US20070103060

Osminum(III) complexes		Chem. Mater. 17, 3532 (2005)

Ruthenium(II) complexes		Adv. Mater. 17, 1059 (2005)

Rhenium (I), (II), and (III) complexes		US20050244673

Green dopants

Iridium(III) organometallic complexes	and its derivatives	Inorg. Chem. 40, 1704 (2001)

		US20020034656

		U.S. Pat. No. 7,332,232

		US20090108737

		WO2010028151

		EP1841834B

		US20060127696

		US20090039776

		U.S. Pat. No. 6,921,915

		US20100244004

		U.S. Pat. No. 6,687,266

		Chem. Mater. 16, 2480 (2004)

		US20070190359

		US 20060008670 JP2007123392

		WO2010086089, WO2011044988

		Adv. Mater. 16, 2003 (2004)

		Angew. Chem. Int. Ed. 2006, 45, 7800

		WO2009050290

		US20090165846

		US20080015355

		US20010015432

		US20100295032

Monomer for polymeric metal organometallic compounds		U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598

Pt(II) organometallic complexes, including polydentated ligands		Appl. Phys. Lett. 86, 153505 (2005)

		Appl. Phys. Lett. 86, 153505 (2005)

		Chem. Lett. 34, 592 (2005)

		WO2002015645

		US20060263635

		US20060182992 US20070103060

Cu complexes		WO2009000673

		US20070111026

Gold complexes		Chem. Commun. 2906 (2005)

Rhenium(III) complexes		Inorg. Chem. 42, 1248 (2003)

Osmium(II) complexes		U.S. Pat. No. 7,279,704

Deuterated organometallic complexes		US20030138657

Organometallic complexes with two or more metal centers		US20030152802

		U.S. Pat. No. 7,090,928

Blue dopants

Iridium(III) organometallic complexes		WO2002002714

		WO2006009024

		US20060251923 US20110057559 US20110204333

		U.S. Pat. No. 7,393,599, WO2006056418, US20050260441, WO2005019373

		U.S. Pat. No. 7,534,505

		WO2011051404

		U.S. Pat. No. 7,445,855

		US20070190359, US20080297033 US20100148663

		U.S. Pat. No. 7,338,722

		US20020134984

		Angew. Chem. Int. Ed. 47, 4542 (2008)

		Chem. Mater. 18, 5119 (2006)

		Inorg. Chem. 46, 4308 (2007)

		WO2005123873

		WO2005123873

		WO2007004380

		WO2006082742

Osmium(II) complexes		U.S. Pat. No. 7,279,704

		Organometallics 23, 3745 (2004)

Gold complexes		Appl. Phys. Lett. 74, 1361 (1999)

Platinum(II) complexes		WO2006098120, WO2006103874

Pt tetradentate complexes with at least one metal- carbene bond		U.S. Pat. No. 7,655,323

Exciton/hole blocking layer materials

Bathocuprine compounds (e.g., BCP, BPhen)		Appl. Phys. Lett. 75, 4 (1999)

		Appl. Phys. Lett. 79, 449 (2001)

Metal 8-hydroxyquinolates (e.g., BAlq)		Appl. Phys. Lett. 81, 162 (2002)

5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole		Appl. Phys. Lett. 81, 162 (2002)

Triphenylene compounds		US20050025993

Fluorinated aromatic compounds		Appl. Phys. Lett. 79, 156 (2001)

Phenothiazine-S-oxide		WO2008132085

Silylated five-membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles		WO2010079051

Aza-carbazoles		US20060121308

Electron transporting materials

Anthracene- benzoimidazole compounds		WO2003060956

		US20090179554

Aza triphenylene derivatives		US20090115316

Anthracene-benzothiazole compounds		Appl. Phys. Lett. 89, 063504 (2006)

Metal 8-hydroxyquinolates (e.g., Alq₃, Zrq₄)		Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107

Metal hydroxybenoquinolates		Chem. Lett. 5, 905 (1993)

Bathocuprine compounds such as BCP, BPhen, etc		Appl. Phys. Lett. 91, 263503 (2007)

		Appl. Phys. Lett. 79, 449 (2001)

5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzoimidazole)		Appl. Phys. Lett. 74, 865 (1999)

		Appl. Phys. Lett. 55, 1489 (1989)

		Jpn. J. Apply. Phys. 32, L917 (1993)

Silole compounds		Org. Electron. 4, 113 (2003)

Arylborane compounds		J. Am. Chem. Soc. 120, 9714 (1998)

Fluorinated aromatic compounds		J. Am. Chem. Soc. 122, 1832 (2000)

Fullerene (e.g., C60)		US20090101870

Triazine complexes		US20040036077

Zn (N{circumflex over ( )}N) complexes		U.S. Pat. No. 6,528,187

EXPERIMENTAL

Compound Examples

A. Synthesis of Compound 13-H

A.1. Synthesis of 2-([1,1′-biphenyl]-2-yl)-6-methoxypyridine

2-biphenylboronic acid (4 g, 20 mmol), and 2-bromo-6-methoxypyridine (2.4 g, 20 mmol) were mixed in 250 mL of toluene and 30 mL of deionized water. The resulting solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.3 g, 0.3 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.6 g, 1.5 mmol) and K₃PO₄(13.6 g, 64 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the aqueous layer was removed from the reaction mixture. The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. White solid was recrystallized from hexane, yielding 4.2 g (80%) of 2-([1,1′-biphenyl]-2-yl)-6-methoxypyridine.

A.2 Synthesis of 2-methoxydibenzo[f,h]quinoline

2-([1,1′-biphenyl]-2-yl)-6-methoxypyridine (2.0 g, 7.7 mmol), iodine (3.0 g, 11.8 mmol) and propylene oxide (3 mL) and 250 mL of toluene were charged into a double-walled quartz photochemical reactor equipped with a medium pressure mercury lamp. The solution was bubbled with nitrogen for 15 min. It was then irradiated for 24 h. After cooling, the reaction mixture was quenched by sodium sulfite and the organic layer was dried over magnesium sulfate and filtered. The solvent was then evaporated and the residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. White solid was recrystallized from methanol, yielding 1.5 g (75%) of 2-methoxydibenzo[f,h]quinoline.

A.3. Synthesis of 2-hydroxydibenzo[f,h]quinoline

A mixture of 2-methoxydibenzo[f,h]quinoline (1 g, 3.8 mmol) and pyridine hydrochloride (4.5 g, 38 mmol) was heated at 220° C. for 2 hours under nitrogen. The solution was cooled and water was added, resulting in the formation of a white precipitate, which was collected by vacuum filtration, washed with water, and dried in vacuo, yielding 0.9 g (96%) of 2-hydroxydibenzo[f,h]quinoline.

A.4. Synthesis of dibenzo[f,h]quinolin-2-yl trifluoromethanesulfonate

To a cooled solution (0° C.) of 2-hydroxydibenzo[f,h]quinoline (0.9 g, 3.6 mmol), pyridine (1.2 mL) and 200 mL of dichloromethane was added dropwise trifluoromethanesulfonyl anhydride (3.5 mL) under nitrogen. The reaction mixture was allowed to stir overnight at room temperature. The reaction mixture was cooled to 0° C. and quenched by water, the organic layer was dried over magnesium sulfate and filtered through filter paper. The solvent was then evaporated and the residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. The white solid was recrystallized from methanol, yielding 1.2 g (88%) of precursor dibenzo[f,h]quinolin-2-yl trifluoromethanesulfonate.

A.A. Example of Synthesis of Compound 13-H Using Precursor dibenzo[f,h]quinolin-2-Yl trifluoromethanesulfonate

9-phenyl-9H,9′H-3,3′-bicarbazole (0.2 g, 0.48 mmol) and dibenzo[f,h]quinolin-2-yl trifluoromethanesulfonate (0.2 g, 0.49 mmol) were mixed in 70 mL of dry toluene. The resulting solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.02 g, 0.02 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.04 g, 0.08 mmol) and ^tBuONa (0.15 g, 1.5 mmol) were added in sequence. The mixture was refluxed overnight under nitrogen. After cooling, the reaction mixture was filtered through celite/silica pad and the solvent was evaporated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. The solid was recrystallized from methanol to yield 0.14 g (45%) of Compound 13-H.

A.B. Example of Synthesis of Compound 9-H Using Precursor dibenzo[f,h]quinolin-2-Yl trifluoromethanesulfonate

N¹,N¹,N⁴-triphenyl-N⁴-(4-(phenylamino)phenyl)benzene-1,4-diamine (0.25 g, 0.48 mmol) and dibenzo[f,h]quinolin-2-yl trifluoromethanesulfonate (0.2 g, 0.49 mmol) were mixed in 70 mL of dry toluene. The resulting solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.02 g, 0.02 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.04 g, 0.08 mmol) and ^tBuONa (0.15 g, 1.5 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the reaction mixture was filtered through celite/silica pad and the solvent was evaporated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. The solid was recrystallized from methanol, yielding 0.16 g (47%) of Compound 9-H.

A.C. Example of Synthesis of Compound 82-H Using Precursor dibenzo[f,h]quinolin-2-yl trifluoromethanesulfonate

Diphenylamine (0.08 g, 0.48 mmol) and dibenzo[f,h]quinolin-2-yl trifluoromethanesulfonate (0.2 g, 0.49 mmol) were mixed in 70 mL of dry toluene. The resulting solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.02 g, 0.02 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.04 g, 0.08 mmol) and ^tBuONa (0.15 g, 1.5 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the reaction mixture was filtered through celite/silica pad and the solvent was evaporated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. The solid was recrystallized from methanol, yielding 0.09 g (47%) of Compound 82-H.

B. Synthesis of Compound 129-H

B.1. Synthesis of 5-([1,1′-biphenyl]-2-yl)-2-methoxypyrimidine

2-biphenylboronic acid (4.0 g, 20.0 mol), and 5-bromo-2-methoxypyrimidine (2.4 g, 20.0 mmol) were mixed in 250 mL of toluene and 30 mL of deionized water. The solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.3 g, 0.3 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.6 g, 1.5 mmol) and K₃PO₄(13.6 g, 64 mmol) were added in sequence. The mixture was refluxed overnight under nitrogen. After cooling, the aqueous layer was removed from the reaction mixture, the organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. The white solid obtained was recrystallized from hexane, yielding 4.2 g (80%) of product.

B.2. Synthesis of 2-methoxydibenzo[f,h]quinazoline

In a 250 mL round-bottom flask equipped with a nitrogen inlet and a stir bar, 5-([1,1′-biphenyl]-2-yl)-2-methoxypyrimidine (4.0 g, 15.3 mmol) was dissolved in anhydrous methylene chloride (100 mL). Iron(III) chloride (5.0 g, 30.6 mmol) was then added, and the mixture was stirred overnight. An additional two equivalents of iron(III) chloride were added, and the reaction reached completion within one hour. Methanol and water were added to the mixture and the organic layer was separated, dried over magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography with 60/40 methlyene chloride/hexane as the eluent to give 3.5 g of a light yellow solid which was recyrstallized from 700 mL of methanol, yielding 3 g of 2-methoxydibenzo[f,h]quinazoline.

B.3. Synthesis of 2-hydroxydibenzo[f,h]quinazoline

A mixture of 2-methoxydibenzo[f,h]quinazoline (1.0 g, 3.8 mmol) and pyridine hydrochloride (4.5 g, 38.0 mmol) was heated at 220° C. for 2 h under nitrogen. The solution was cooled and water was added, resulting in the formation of a white precipitate, which was collected by vacuum filtration, washed with water, and dried in vacuo to yield 0.9 g (96%) of 2-hydroxydibenzo[f,h]quinazoline.

B.4. Synthesis of precursor dibenzo[f,h]quinazolin-2-yl trifluoromethanesulfonate

To a cooled solution (0° C.) of 2-hydroxydibenzo[f,h]quinazoline (0.9 g, 3.6 mmol), pyridine (1.2 mL) and 200 mL of dy dichloromethane was added dropwise trifluoromethanesulfonyl anhydride (3.5 mL). The reaction mixture was allowed to stir overnight at room temperature. The reaction mixture was cooled to 0° C. and quenched by water. The organic layer was dried over magnesium sulfate and filtered. The solvent was evaporated and the residue was purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. The white solid obtained was recrystallized from methanol, yielding 1.2 g (88%) of product.

B.A. Synthesis of Compound 129-H Using Precursor dibenzo[f,h]quinazolin-2-yl trifluoromethanesulfonate

9-phenyl-9′-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H,9′H-3,3′-bicarbazole (0.5 g, 0.8 mmol), potassium phosphate tribasic (0.5 g, 2.4 mmol) and dibenzo[f,h]quinazolin-2-yl trifluoromethanesulfonate (0.3 g, 0.8 mmol) were mixed in 70 mL of toluene, 10 mL of deionized water and 10 mL of ethanol. To the solution was bubbled nitrogen for 15 min. Pd₂(dba)₃(0.3 g, 0.3 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.6 g, 1.4 mmol) were added. The mixture was refluxed for 2 days under nitrogen. After cooling, the aqueous layer was discarded. The organic layer was filtered through celite/silica pad and concentrated. The residue was purified by column chromatography using THF:hexane (1:9, v/v) as the eluent. The residue was purified by column chromatography using DCM:hexane (1:1, v/v) as the eluent. The solid obtained was recrystallized from methanol, yielding 0.12 g (21%) of product.

C. Synthesis of Compound 15-H

C.1. Synthesis of 5-([1,1′-biphenyl]-2-yl)-2-chloropyrimidine

2-biphenylboronic acid (4.0 g, 20.0 mol), and 5-bromo-2-chloropyrimidine (2.4 g, 20.0 mmol) were mixed in 250 mL of toluene and 30 mL of deionized water. To the solution was bubbled nitrogen while 15 min. Pd₂(dba)₃(0.3 g, 0.3 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.6 g, 1.5 mmol) and K₃PO₄(13.6 g, 64 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the aqueous layer was removed from the reaction mixture. The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography using DCM:hexane (1:4, v/v) as eluent. The white solid obtained was recrystallized from hexane, yielding 4.2 g (80%) of product.

C.2. Synthesis of Precursor 2-chlorodibenzo[f,h]quinazoline

A Iron(III) chloride (5.0 g, 30.6 mmol) was then added to 5-([1,1′-biphenyl]-2-yl)-2-chloropyrimidine (4.0 g, 15.3 mmol) in anhydrous methylene chloride (100 mL). and the mixture was stirred overnight. An additional two equivalents of iron(III) chloride were added, and the reaction reached completion within one hour. Methanol and water were added to the mixture and the organic layer was separated, dried over magnesium sulfate, and concentrated. The crude product was purified by column chromatography with 60/40 methlyene chloride/hexane as the eluent to give 3.5 g of a light yellow solid which was recyrstallized from 700 mL of methanol, yielding 3.0 g of 2-chlorodibenzo[f,h]quinazoline.

C.A. Synthesis of Compound 15-H Using the Precursor 2-chlorodibenzo[f,h]quinazoline

9-phenyl-9H,9′H-3,3′-bicarbazole (0.31 g, 0.76 mmol) and sodium hydride (0.05 g, 1.2 mmol) were mixed in 30 mL of dry dimethylformamide. The mixture was stirred for 1 h. 2-chlorodibenzo[f,h]quinazoline (0.2 g, 0.75 mmol) were added and the mixture was stirred overnight. The solvent was removed and the residue was then purified by column chromatography using THF:hexane (1:4, v/v) as the eluent. The solid obtained was recrystallized from methanol, yielding 0.15 g (32%) of product.

D. Synthesis of Compound 4-H

D.1. Synthesis of 2-([1,1′-biphenyl]-2-yl)-5-methoxypyrazine

2-biphenylboronic acid (4.0 g, 20 mol), and 2-bromo-5-methoxypyrazine (3.1 g, 16.2 mmol) were mixed in 150 mL of toluene and 50 mL of ethanol. The solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.46 g, 0.5 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.6 g, 1.5 mmol) and K₃PO₄(12.9 g, 60.6 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the aqueous layer was removed from the reaction mixture. The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography using EA:hexane (1:1, v/v) as the eluent, yielding 2.7 g (64%) of a white solid as the product.

D.2. Synthesis of 2-methoxydibenzo[f,h]quinoxaline

2-([1,1′-biphenyl]-2-yl)-5-methoxypyrazine (2.5 g, 9.6 mmol), iodine (3.6 g, 14.4 mmol), propylene oxide (25 ml) and 250 mL toluene were charged into a double-walled quartz photochemical reactor equipped with a medium pressure mercury lamp. The solution was bubbled with nitrogen for 15 min. It was then irradiated for 24 h. After cooling, the reaction mixture was quenched with sodium sulfite and the organic layer was dried over magnesium sulfate and filtered. The solvent was then evaporated and the residue was purified by column chromatography using EA:hexane (1:1, v/v) as the eluent, yielding 1.89 g (76%) of 2-methoxydibenzo[f,h]quinoxaline.

D.3. Synthesis of dibenzo[f,h]quinoxalin-2-ol

A mixture of 2-methoxydibenzo[f,h]quinazoline (1.3 g, 5.1 mmol) and pyridine hydrochloride (5.8 g, 50.6 mol) was heated at 220° C. for 2 hours under nitrogen. The solution was cooled and water was added, resulting in the formation of a white precipitate, which was collected by vacuum filtration, washed with water, and dried in vacuo, yielding 1.2 g (97%) of dibenzo[f,h]quinoxalin-2-ol.

D.4. Synthesis of Precursor dibenzo[f,h]quinoxalin-2-yl trifluoromethanesulfonate

To a cooled solution (0° C.) of dibenzo[f,h]quinoxalin-2-ol (1.2 g, 4.9 mmol), pyridine (60 mL) and 15 mL of anhydrous dichloromethane was added dropwise trifluoromethanesulfonic anhydride (2 mL) under nitrogen. The reaction mixture was allowed to stir overnight at room temperature. The reaction mixture was cooled to 0° C. and quenched by deionized water. The organic layer was dried over magnesium sulfate, filtered and concentrated and the residue was then purified by column chromatography using toluene:hexane (1:4, v/v) as the eluent, yielding 0.6 g (32%) of dibenzo[f,h]quinoxalin-2-yl trifluoromethanesulfonate.

D.A. Synthesis of Compound 4-H Using Precursor dibenzo[f,h]quinoxalin-2-yl trifluoromethanesulfonate

N¹,N¹,N⁴-triphenylbenzene-1,4-diamine (0.089 g, 0.3 mmol), and dibenzo[f,h]quinoxalin-2-yl trifluoromethanesulfonate (0.1 g, 0.3 mmol) were mixed in 10 mL of xylene. The solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.012 g, 0.01 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.011 g, 0.03 mmol) and sodium t-butoxide (0.025 g, 0.3 mmol) were added. The mixture was refluxed for 2 days under nitrogen. After cooling, the reaction mixture was filtered and the solvent was evaporated. The residue was then purified by column chromatography using gradient from hexane to toluene:hexane (1:1, v/v) as eluent, yielding 0.86 g (58%) of Compound 4-H.

E. Synthesis of Compound 16-H and 457-H

E.1. Synthesis of Precursor 2-bromodibenzo[f,h]quinoxaline

Dibenzo[f,h]quinoxalin-2-yl trifluoromethanesulfonate (0.49 g, 1.2 mmol) and tetrabutylammonium bromide (0.83 g, 25.8 mmol) were refluxed in 20 ml toluene under nitrogen for 24 h. The solution was dried and column chromatographed using toluene:hexane (1:4, v/v) as the eluent, yielding 0.35 g (87%) of 2-bromodibenzo[f,h]quinoxaline.

E.A. Example of Synthesis of Compound 16-H Using Precursor 2-bromodibenzo[f,h]quinoxaline

9-phenyl-9H,9′H-3,3′-bicarbazole (0.15 g, 0.4 mmol), and 2-bromodibenzo[f,h]quinoxaline (0.1 g, 0.3 mmol) were mixed in 5 mL toluene. The solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.016 g, 0.02 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.015 g, 0.04 mmol) and sodium t-butoxide (0.035 g, 0.4 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the reaction mixture was filtered through celite/silica pad and the filtrate was concentrated under vacuum. The residue was then purified by column chromatography using THF:hexane (1:1, v/v) as the eluent, yielding 0.13 g (57%) of Compound 16-H.

E.B. Example of Synthesis of Compound 457-H Using Precursor 2-bromodibenzo[f,h]quinoxaline

N,9-diphenyl-9H-carbazol-3-amine (0.52 g, 1.6 mmol), and dibenzo[f,h]quinolin-2-yl trifluoromethanesulfonate (0.53 g, 1.6 mmol) were mixed in 15 mL toluene. The solution was bubbled with nitrogen for 15 min. Pd₂(dba)₃(0.071 g, 0.08 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.064 g, 0.16 mmol) and sodium t-butoxide (3.3 g, 3.4 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the reaction mixture was filtered through celite/silica pad and the filtrated was concentrated under vacuum. The residue was purified by column using toluene:hexane (2:3, v/v) as the eluent, yielding 0.28 g (32%) of Compound 457-H.

Alternate Novel Method for Synthesis of Compounds of Formula 1

As disclosed herein, Formula 1 is represented by
wherein X₁to X₁₂is independently selected from the group consisting of C—R and N, wherein each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. The inventors have also discovered that the syntheses of compounds of Formula 1 by ring closing of compounds of Formula Y
can be achieved by an improved novel method instead of using the traditional method using UV, iodine and propylene oxide.
In the novel method, the ring closure is achieved by the use of light (UV) and cyclohexene. Although light (UV) and cyclohexene was shown to be effective in ring closure of stilbenes to form phenanthrenes (Bull. Chem. Soc. Jpn. Vol. 82, No. 9, 1182), it was unexpected that such a mild system would work for the ring closure of compounds of Formula Y to form compounds of Formula 1. Because of the steric effect, the two rings where the C—C bond formation occurs are more out of plane of each other in compounds of Formula Y than in stilbenes (unsubstituted at the double bond as reported in Bull. Chem. Soc. Jpn. Vol. 82, No. 9, 1182). As a result, only strong oxidants such as iodine and oxygen have been shown to be effective in photocyclization of compounds of Formula Y to form compounds of Formula 1. In this discovery, it was unexpectedly found that cyclohexene, although a weak oxidant, was effective in photocyclization of compounds of Formula Y to form compounds of Formula 1.

F.1. Synthesis of Precursor 2-methoxydibenzo[f,h]quinolone Using the Novel Method

2-([1,1′-biphenyl]-2-yl)-6-methoxypyridine (1.0 g, 3.7 mmol), cyclohexene (2 mL) and toluene (250 mL) were charged into a double-walled quartz photochemical reactor equipped with a medium pressure mercury lamp. The solution was bubbled with nitrogen for 15 min. It was then irradiated with UV for 24 hrs. After cooling, the solvent was evaporated and the residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent. The white solid obtained was recrystallized from methanol, yielding 0.7 g (75%) of product.

F.2. Synthesis of 4,4′-(4-methoxy-1,2-phenylene)dipyridine

Pyridine-4-ylboronic acid (7.5 g, 61.0 mmol), and 1,2-dibromo-4-methoxybenzene (4.1 g, 15.3 mmol) were mixed in 80 mL of dimethoxyethane. The solution was bubbled with nitrogen for 15 min. Pd(PPh₃)₄(3.5 g, 3.1 mmol), triphenylphosphine (2.5 g, 6.1 mmol) and cesium fluoride (9.7 g, 45.8 mmol) were added. The mixture was refluxed overnight under nitrogen. After cooling, the aqueous layer was removed from the reaction mixture. The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography using THF:hexane (7:3, v/v) as the eluent. The white solid obtained was recrystallized from hexane, yielding 3.3 g (82%) of product.

G.1. Synthesis of Precursor 6-methoxybenzo[f][2,9]phenanthroline

4,4′-(4-methoxy-1,2-phenylene)dipyridine (0.5 g, 1.9 mmol), cyclohexene (2 ml) and toluene (250 mL) were charged into a double-walled quartz photochemical reactor equipped a medium pressure mercury lamp. The solution was bubbled with nitrogen for 15 min. It was then irradiated for 2 days. After cooling, the solvent was then evaporated and the residue was purified by column chromatography using THF:hexane (7:3, v/v) as the eluent. The white solid was recrystallized from methanol, yielding 0.3 g (69%) of product.
This new method avoids light absorption by iodine, eliminates the formation of acidic HI and polymerized propylene oxide. Furthermore, propylene oxide evaporates easily due to its low boiling point of (b.p.=34° C.), making the control of exact equivalents in the reaction difficult. One the other hand, cyclohexene has a much high boiling point (b.p.=83° C.) and does not evaporate easily, allowing the control of exact equivalents in the reaction.
Experimental Data:
Electrochemistry, photoluminescence, photoluminescence quantum yield (PLQY) and solvatochromism experiments were carried out for samples of the donor-acceptor compound samples Compound 9, 13 and 82. The data is summarized below in Table 2. Small molecule host (Compound B and Compound D) doped films were fabricated by vacuum thermal evaporation on quartz substrates. Poly(methyl methacrylate) (PMMA) and polystyrene (PS) doped film were fabricated by solution drop casting on quartz substrates.

TABLE 2

	Oxidation and			Em_maxat	Em_maxat	Em_maxat
	Reduction			RT in	RT in	RT in
	potential, vs	PLQY, 5%	Em_max(host)	2Me—THF	toluene	hexane
Cmpd	Fc/Fc⁺ [V]	doping (host)	[nm]	[nm]	[nm]	[nm]

9-H	E_ox= 0.13 (R)	76% (Cmpd B)	473 (Cmpd B)	536	507	474
	E_red= 2.70 (R)	69% (Cmpd D)	477 (Cmpd D)
457-H	E_ox= 0.45 (R)	52% (PMMA)	455 (PMMA)	430	420	406
	E_red= −2.70 (R)	41% (PS)	455 (PMMA)
		36% (Cmpd D)	450 (Cmpd D)
4-H	E_ox= 0.34 (R)	45% (PMMA)	539 (PMMA)	626	597	536
	E_red= −2.23 (R)
129-H	E_ox= 0.59 (IR)	34% (PMMA)	448 (PMMA)	481	432	392
	E_red= −2.23 (IR)	63% (Cmpd D)	437 (Cmpd D)
15-H	E_ox= 0.64 (R)	44% (PMMA)	467 (PMMA)	504	475	444
	E_red= −2.13 (R)
16-H	E_ox= 0.65 (R)	69% (PMMA)	494 (PMMA)	515	483	436
	E_red= −2.03 (R)

(R = reversible, IR = irreversible)

Table 2 shows that the emission of the donor-acceptor compounds of Formula 1 consists of charge transfer origins as evidenced by the solvatochromism. Donor-acceptor emitters of Formula 1 can be efficient luminescent compounds. The PLQY of Compound 9-H in mCBP is 69%. When Compound 9-His doped in Compound B, the PLQY is 76%. Compound 9-H shows reversible redox, a desirable feature for stable OLEDs. The PLQY of Compound 129-H in mCBP is 63%. The compounds can produce blue luminescence as shown. The acceptor strength in the donor-acceptor compounds can be tuned by varying the position and number of nitrogens in the triphenylene such as in Formulae 2-19 whereas the donor strength can be tuned by using various electron donating groups such as in D1-D140. Consequently, the CT emission can be tuned.

Device Examples

In the OLED experiment, all device examples were fabricated by high vacuum (<10-7 Torr) thermal evaporation. The anode electrode is ˜800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) and a moisture getter was incorporated inside the package.
The organic stack of the Device Example 1 consists of sequentially, from the ITO surface, 100 Å of LG101 (purchased from LG Chem, Korea) as the hole injection layer (HIL), 300 Å of Compound A as the hole transporting layer (HTL), 300 Å of Compound B doped with 5% of Compound 9-H as the emissive layer (EML), 50 Å of Compound C as the ETL2 and 400 Å of LG-201 as the ETL1. The maximum external quantum efficiency is 9.6%. CIE is 0.171, 0.317.
Device Example 2 is the same as Device Example 1 except that Compound B is replaced with Compound D. The maximum external quantum efficiency is 8.0%. CIE is 0.173, 0.335.
The high device external quamtum efficiency (EQE) of Device Examples 1 and 2 shows that donor-acceptor compounds of Formula 1 are efficient emitters for OLEDs. The high device external quamtum efficiency also suggests that triplet excition may be converted into emissive singlet excition via the delayed fluorescence mechanism.
It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

Claims

We claim:

1. A compound having the formula:

wherein X₁to X₁₂is independently selected from the group consisting of C—R and N;

wherein at least one of X₁to X₁₂is N;

wherein each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

at least one of the R comprises a donor group with at least two electron-donating nitrogens.

2. The compound of claim 1, wherein the compound is selected from the group consisting of

wherein R₁to R₁₂are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;

at least one of R₁to R₁₂is

wherein L is a linker,

m is 1 or 0,

n≧1; and

wherein Donor is an electron donating group containing at least two electron-donating nitrogens and Donors can be different when n>1.

3. The compound of claim 2, wherein Donor is selected from the group consisting of:

wherein S₁to S₇represent mono, di, tri, tetra or penta substitutions with hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

4. The compound of claim 2, wherein L is one of

wherein A₁to A₂represent mono, di, tri or tetra substitutions with hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

5. The compound of claim 1, wherein the compound is one of

6. The compound of claim 5, wherein S₁to S₆and A₁-A₂are H.

7. A first device comprising a first organic light emitting device, further comprising:

an anode;

a cathode; and

an organic emissive layer, disposed between the anode and the cathode;

wherein the organic emissive layer comprises a first emitting compound having a structure according to Formula 1

at least one of X₁to X₁₂is N;

each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

wherein at least one of the R comprises a donor group with at least one electron-donating nitrogen.

8. The first device of claim 7, wherein the first emitting compound is selected from the group consisting of

at least one of R₁to R₁₂is

wherein L is a linker,

m is 1 or 0,

n≧1; and

wherein Donor is an electron donating group containing at least one electron-donating nitrogen and Donors can be different when n>1.

9. The first device of claim 8, wherein Donor is selected from the group consisting of:

10. The first device of claim 9, wherein L is one of

11. The first device of claim 7, wherein the first emitting compound is one of

12. The first device of 11, wherein S₁to S₆and A₁-A₂are H.

13. The first device of claim 7, wherein the first device emits a luminescent radiation at room temperature when a voltage is applied across the organic light emitting device;

wherein the luminescent radiation comprises a delayed fluorescence process.

14. The first device of claim 7, wherein the emissive layer further comprises a first phosphorescent emitting material.

15. The first device of claim 14, wherein the emissive layer further comprises a second phosphorescent emitting material.

16. The first device of claim 7, wherein the emissive layer further comprises a host material.

17. The first device of claim 14, wherein the first device emits a white light at room temperature when a voltage is applied across the organic light emitting device.

18. The first device of claim 17, wherein the first emitting compound emits a blue light with a peak wavelength of about 400 nm to about 500 nm.

19. The first device of claim 17, wherein the first emitting compound emits a yellow light with a peak wavelength of about 530 nm to about 580 nm.

20. The first device of claim 7, wherein the first device comprises a second organic light emitting device;

wherein the second organic light emitting device is stacked on the first organic light emitting device.

21. The first device of claim 7, wherein the first device is a consumer product.

22. The first device of claim 7, wherein the first device is an organic light-emitting device.

23. The first device of claim 7, wherein the first device is a lighting panel.

24. The first device of claim 7, wherein at least one of the R comprises a donor group with at least two electron-donating nitrogens.

25. A formulation comprising a compound according to claim 1.

26. A method of making compounds of Formula 1 by a ring closure reaction of compounds of Formula Y, wherein Formulas 1 and Y are

wherein X₁to X₁₂is independently selected from the group consisting of C—R and N; wherein each R is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, said method comprising:

preparing a solution of a quantity of a compound of Formula Y in a solution containing cyclohexene; and

irradiating the solution with UV light.